Investigation of benzene adsorption on different metal surfaces closer to a practical system appears to be a very important intermediate stage to utilize the conclusion obtained on single- crystal surfaces. In this paper, we studied the electrochemical adsorption behaviors of benzene on roughened Pt group electrodes using surface enhanced Raman spectroscopy (SERS). The effects of potential, surface roughness, and benzene concentration were investigated. Significant difference in surface Raman spectra of benzene on Ru, Rh, Pd, and Pt surfaces were found. On Pt surfaces, the parallel-chemisorbed benzene, the vertical dissociated chemi-sorbed benzene, and the physisorbed benzene were observed, evidenced by the ring vibration mode appearing at 872, 1012, and 991 cm(-1), respectively. On Pd, only parallel-chemisorbed benzene and physisorbed benzene were found. On Rh and Ru, the SERS signals were mainly from the parallel-chemisorbed benzene, with an extremely weak signal from the physisorbed benzene. The potential dependent study reveals that the parallel-chemisorbed species interacts strongest with the substrate, while the physisorbed species can be easily removed at positive potentials. The models for the adsorbed benzene were given to account for the different types of benzene on these Pt group metals. The difference in the atomization heat of the four metals was used to interpret the different interaction strength of benzene with Pt group metals.